Dresden 2026 – wissenschaftliches Programm

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CPP: Fachverband Chemische Physik und Polymerphysik

CPP 46: Poster II

CPP 46.61: Poster

Donnerstag, 12. März 2026, 09:30–11:30, P5

Benchmarking bond dissociation energies with plane-wave pseudopotential and Gaussian all-electron methods — •Yue Pan¹, Jochen Heil², Ali Karimi², and Arash Mostofi¹ — ¹Imperial College London, South Kensington Campus, London, SW7 2AZ, UK — ²Continental Reifen Deutschland GmbH, Hanover, Germany

Accurate homolytic bond dissociation energies (BDE) are important for understanding bond breaking processes in molecules. They are also frequently used to benchmark the accuracy of different method for electronic-structure calculations. Most calculations of BDE focus on datasets of small gas-phase molecules and, accordingly, are carried out with localised-orbital methods, while systematic comparisons to periodic plane-wave DFT remain scarce. This is relevant for modelling interfacial failure processes in hybrid systems such as polymer nanocomposites, in which molecules are attached to inorganic surfaces, and it becomes less clear which method is more suitable from the perspective of accuracy and efficiency.

In this work, we benchmark the performance of two widely used approaches for DFT calculations, namely the plane-wave basis pseudopotential methods and Gaussian all-electron methods. We use C*C bond dissociation in gas phase hydrocarbons and surface-anchored molecules. We then compare our calculated BDEs with theoretical results obtained from highly accurate quantum chemistry methods and experimental values. Our work represents a step towards a better understanding of bond breaking and interfacial failure in materials.

Keywords: Bond dissociation energies; Density functional theory; Plane-wave pseudopotential methods; All-electron Gaussian calculations